Halogenated anthraquinone acridone and the process of preparing it



Patented Aug. 29, 1933 HALQGENATED ANTHitIQQiI'r-NONEIAORL DONE THE moonssor-rnnmnmd Max Albert Kimzt Mannheini; and-K V and Erich Berthold, Ludwigshafn-on-the-y lthineyGermany, a'ssignors to General Aniline York, N. Y a COI'PQFZlfiOIlOf;

V Thetpresent invent'ion relateslto gan 'irnproyed process of producing at dyestufisof th'e acridone series.

We have found pounds of the general iormulaz e V I Z I ;RN"RO in which Rand R stand for aro natic, isoor heterocyclic radicles which may be substituted Li and of whieh at least one'is yattable andjR is' unsubstituted'in an r group a'ndt Yrf or an alcohol 'o'r phenol a I or an amino orsubs'titutedarniho group; vPreferably'" the esters 0f] thers'aid kindaiie" em ZQL-ployed in the halogenation proee ss orthol-carboxylic acid j coi'rnp ernployed the initial materials mafbei Prepared for' ex -f I ample as follows'zs by" condensation of aromatic j carboxylic acid deriyativeswhich arqneg ajti lyj' .25 substituted in the ortho position toflthensubstie tuted carboxylic tacid group with aromatic" amines having at least one ortho position to the a o oup m eror y conden a i n Q r matic ortho aniinocarboxylic :der vamves with negn stituehts free; wn rebyi n fall cases a of i e t m on nts m s vatting. j'Condens ation products 3 1. describedfor examplef ;th applicat on sert-iqo one; pyranthrone, TI dibenzanthroneg benzan- 5 thronepyrazolanthrone, anthraquinonequinoline;

di'pyrazolanthronyl, pyrimidine; pyrirn'idon, an;

thraquinoneazine and flavanthronet E"- The halogenation may be carried of the halogens chlorineand bromine proper and n .5 by agents supplying these halogens, such as for example phosphorus halides or sulphur halides.

Thehalogenation carriedout either in :the ab: sence oiany diluentor in an" inert organicdilute ing medium,. preferablyv inan inert; aromatic diluting medium of high-boiling point, such as.

. npplicationl fiovenib' A 494,802, and in qermany November that very yaluableivat dyestuffs of the acridone series containing halogen are ob-" I tained by treating with halogen 'or agents sup-- plying halogen; iminoortho-carboxylic acid comreaction.

vThe products 'or tho position to the imino dicle' Q are, forexample, copp out'by means Greens;

nitrobenz ene, hal t e-l ke.- 'An dd lino'wn h an gane'se, mercury, g'ant imony an(ll-their halides, or. non metals, such 'tion oi one oraseyeral 'ot the earth metal oxides, Inay,- a1so been1ployed the chlorine or j bromine or chlorine and bromine and are usually obtained ingood'yields and inj astate of good purity. Theyidye the vegetable fibre a greatvariety'of s able intermediate products dyestuffs. The shade'sob stuffs and the properties v thereof [can ofthflbq for the preparation of I rivatives ,obtained with agents Which-split off halogenfor hydrogen halide;j Such's'plitting or: isloite al a ef c ed h n v t 'nstt u rode c i at t m e a u es bove bout 0?: .Q- -;Qr 'nay be. brought" about in organic solvents by; means 1". a e ts havi a ind in a t n it res-- en p su h met ls an exide on wh fare m de ily reduced, to metals; as de cribed in the copendfor example hydrazine and its derivativesj'hydro- Metals offthe said kind I er, nickel, iron, cobalt, silver" and their oxides or saltsthereof.

the usual methods, as for eggample by-crystallizaetreatment" with oxidizing agents, as for example with sodium hypochlorite, Darby-wa of their oxon'um salts, as forf example by way oitheirl -oxoniumsulph ates. 4 v I The-following examples will further illustrate a hew fi ri rsnnwi s ti n parts; otj the condensation product from di brorno-3 4.8.9-5dibenzopyrener5.10 quinone' :5( ob 3 g t'ainable by brorninating :the saidwdibenzopyrene-ili quinone in chlorosulphonic acid 5111 the presence boxylic acid ethylest'er are suspended in 20 parts,

* v n n i v UN TED P A-TEN 1 g'enbenzenesj, pnthsienjaaa,

los nat on c ta ysts-torexamb e m ta e-j metal, compo'uhdgflfor example iron, 'm'an- I 7 60 'assulphur, phosphorus, iodine and selenium, is often'afdvantageous. A cid-bind-"j a ing agentsZ'asforexample alkali metal oralkar 1;; line earthmetahsalts ofiweak acids or alkaline t 5}; ,I obtainedaccording to. the present invention are acridone derivatives-containing A H hades and afre also valu tained' with .the we,

: Varied or improved bi t i the acridone dequinon'e, dioxindole, hydrazobenzene, glyoggal, .9

If necessary the products may'--bepurified 1 11 tion or by extraction :with organic solvents, I

100* I Th arts-4.

of antimony) and:1+aminoanthraquinoneqz car l l' 1 19m 0. while stirring. firychlori ne' gas is led in until the reaction liquid has become pure .brown redin colour,-which is the caseafter a few hours. The whole is allowed to cool and the reaction productis isolated by filteringby suc tion or. by. distilling off the solvent, if desired under reduced pressure and/or with steam; The

reaction product is a brown red powder'which dissolves in concentrated sulphuricacid giving a'blue red colouration and gives wine-red very 'fast dyeings on the vegetable fibre from, a blue redvat. a

Example? 2 parts of the initial material employed in Ex "ample 1 are heated'in 20parts of initrobenzene,

after the addition of 2 parts of bromine, tofirom 170 to 180C. While stirring until the reaction I liquid has become pure red brown in colour.

The reaction. mixture .is then worked up as described "in Example 'l-.' The resulting reaction products containing bromine is a brown powder; dissolves in concentrated sulphuric acid giving a blue redicolouration and yields very fastred brown dyeings on cotton from a brown violet vat.

c I v rimpze 3 i I 1 part of the product obtainable by condensing 8-chlorbenzanthrone withv 1-'-aminoanthraquin- I 7 b 'ion'eez-carboxylic acid phenyl ester corresponding to the formula? heated to 160 C. in 10 parts of ,trichlorbenzene ;.while stirring; Drychlorine gas is then led; in

and the whole isheated slowly-to boiling. f As soon 'as the-reaction mixture, has become yellow brown it is "allowed to {cool and is worked up as 7 described in Example *1. The reaction product i a gcontainingchlorine obtained in a very good yield corresponds to the formula: a

is an orange crystalline'powder which; dissolves in concentrated sulphuric acid giving a blue red coloration and yields veryfastyellow brown dye ings on cotton from a brown vat.

* agentflf desired in the absence of trichlo rbenzen'e; Reaction products giving similar dyeings are likewise obtained from ;other benzanth'rone am Instead of chlorine," phosphorus pentachloride maybe employed as the chlorinating condensing thraquinonylamino-ortho-carboxylic acid esters bytreating with halogen;

then

-2.1(N -benzacridone filtered on; It is v powder which dissolves in concentrated sulphuric Example 4 A 30 parts of bromine are added; while stirring, at C. to 10 parts of 2.5-dichloro1-anilidoanthraquinone-2-carboxylic acid benzyl ester corresponding to theformula: 0

in 100 parts of nitrobenzene after the addition of a v 1 partofgiodine. The whole is then heated to e180? 0., kept at the same'temperature for several hours, allowed to cool? and the 'dibromo-Bz2Bz5- sponding to the formula:

dichloranthraquinone-2,1ebenzacrid0ne corren precipitated in the fbl m o f red violet m me having a metallic lustre is filtered oiT by suction.

It dissolves in concentrated sulphuric acid giving," an orange colouration, yields a violet blue vatand. dyes" the vegetable fibrerose red shades having.

very good fastnessj A chloro-acridone giving rosedyeings is ob-i 5 tained in'ananalogous manner with chlorine in trichlo'rbenzener l Similarly. afbrominated naph thacridone' isobtai'ned from Lbeta-naphthyl ester with'bromine in: nitrobenzene. i

' Example aminoanthraquinone-2 carboxylic acid ben'zyl,

i210 has of the productfobtainable by condensing j i 1 i 1echloroanthraquinone-2-carboxylic acid i'amide with 3.4.5trichloroaniline are heated'at between.

, 180 and 2001o; in a shaking autoclave wimsoj "parts ofbrominejfor 10 to 12 hours. After coolf ing, the reaction mixture ispoured into water; the:

xcessjof bromine removed by meansj of'sodium I bisulphite andthebromotrichloroanthraquinone ablue red,

acid to givean orange solution-and dyes cotton,

' from a violet vat pink shades. What we claim is ,1; A process ofproducing halogenated a'cridones', which comprises causinga halogenating agent selectedfromthe group consisting of chlo-A rine, bromine and agents. supplying thesehalo compound of the general'formula: v V, V

R'N-R'o in which R stands for an aromatic radicle which gens, to react onan:imino-ortho carboxylic acid tuted in anorthoposition to thefin ino group, R4

stands-for= the anthraquinone nucleus, and Y may be substituted by halogen, but isunsubs'ti-' to react in an inert organic dilutingmediumon stands for a substituent selected from thegroup consisting of alkoxyand phenoxy radicles and the amino group. i

2. A process for producinghalog'enated dones, which comprises causing a halogenating agent selected from the group consisting of chlorine, bromine and agents supplying these halogens,

an imino-ortho-carboxylic acid compound of the general formula: v i t t l '2 R,-NIR --C in which R stands Ior'an aromatic radicle which may be substitutednbyiihalogen, butis unsubsti tuted in an ortho position to the imino group, R

- stands for the anthraquinone nucleus, and LY stands for a substituent selected from the group consisting of 7 alkoxy and phenoxy radicles and the amino group.

i 3. A process of producing halogenated mi: dones, which comprises causing a-"halogenating agent selected from the group consisting'of chlo rine, bromine and agents supplying thesehalogens, to react in an inert aromatic diluting medium: in

V ,the presence of a halogenation catalyst on an imino-ortho-carboxylic acid compound of the generalformulai' n i g 2 R-NB' -C agent selectedfrom the group consisting of chlorine, bromine and agentsjsupplying these halogens, to react in'an inert aromatic dilutingmea. a V I in which 3 stands for an ramme radicle which 7 may be "substituted byhalogenybut is unsubsti-f tuted in an ortho position to theimino group, R

stands for theanthraquinone nucleus, and Y 5 stands for an alkoxy. or phenoxy group;

5. As a new(articleofmanufacture dibromo-Bz 2.5-dichloroanthraquinone -v2 ;1(N) benzacridone I forming red violet needlesi having a metallic j: lustre, dissolving inconcentrated sulphuric acidto. give an orange solution and dyeing cotton from a violet'blue vat rose redfshades. I

ALBERTKUNZ.

KARL KOEBERLE, 1, 3 nron BERTHOLD. 

